201213267 六、發明說明： 【潑^明所屬之》老^持·領^^】 發明領域 本發明涉及將用於薄膜電晶體液晶顯示器的低鐵無鹼 鋁硼矽酸鹽類玻璃的商業生產工藝中所產生的碎玻璃回收 利用為鈉鈣矽酸鹽類太陽能電池基板或蓋子用平板玻璃的 原料，且維持或改善玻璃的製造工藝和物理化學性質的配料。 C先前技術3 發明背景 碎玻璃可定義為不良玻璃、因破碎而不能使用的玻 璃、玻璃)查或玻璃產βσ的破碎品等，這些碎玻璃在玻璃或 玻璃產品製造及加工工藝中必然會產生，而在玻璃行業 中，一般將碎玻璃視為可回收利用為原料的物質加以嚴格 管理。 尤其是，用於薄膜電晶體液晶顯示器的無鹼鋁硼矽酸 鹽類顯示玻璃因起到保護顯示器核心部件並傳遞影像的作 用，因此不能產生哪怕很小的不良率，較之普通窗戶玻璃 或食器玻璃，其製造過程或品質管制非常嚴格。因此，在 所述基板玻璃製造及加工工藝中，若發生溶解不良、外觀 不良及尺寸不良等，需將這些當做不良品廢棄，而在此過 程中產生大量碎玻璃。但為持續保持作為顯示玻璃的品 質，不良顯示玻璃一旦破碎將不再用於顯示玻璃製造過 程，而為廢棄這些碎玻璃將進行淹埋處理等，其量很大。 無鹼鋁硼矽酸鹽類顯示玻璃在成分方面完全不含鹼， 3 201213267 作為雜質存在的Fe203的含量具有0·015重量份（150ppm)〜 〇·〇2重量份(200ppm)的範圍值，從而含量很低，而且，若 Si02、Al2〇3、鹼土（MgO+CaO+SrO+BaO)及B2〇3是主要成 分，則因這些成分可通過熔融過程充分混合，因此，是均 勻性很高的高級玻璃。另外，太陽能電池玻璃是驗石灰矽 酸鹽類玻璃，可根據太陽能電池的種類用於基板或蓋子， 且Si02、CaO ' MgO、Na20是主要成分，而且，為了增加 影響太陽能電池的光電效率的玻璃的太陽光線透過率，將 作為雜質的Fe203的含量限制在〇.〇2重量份(200ppm)以下， 另外，考慮到影響玻璃表面的侵蝕的雨、雪或大氣中的水 分，將Alz〇3的含量調節至1〜2重量份左右，以提高耐候 性。因此，上述低鐵顯示玻璃可通過調節適當的量，成為 數造低鐵驗石灰矽酸鹽類太陽能電池玻璃所需的原料的一 部份，即配料的成分。 人們對回收利用無驗紹硼矽酸鹽類顯示碎玻璃的關注 越來越高’因此’有必要持續開發應用不廢棄碎玻璃而回 收剎用的方法及領域。 作為回收利用無鹼鋁硼矽酸鹽類顯示碎玻璃的現有技 術’有大韓民國註冊專利10-0917269號的“一種以薄膜電晶 雜浪晶顯示器玻璃基板的碎玻璃為原料的蝴石夕酸鹽類長纖 雉戒璃配料”，上述技術涉及回收利用在液晶顯示器用基板 戒璃的製造工藝中碎破璃的方法’其特徵是配料成分中含 有無鹼鋁硼矽酸鹽類顯示碎玻璃，但與在低鐵太陽能電池 ^^痛的應用無關。 201213267 另外，作為回收利用無鹼鋁硼矽酸鹽類顯示碎玻璃的 現有技術，有大韓民國註冊專利10-0929869號的“一種以薄 膜電晶體液晶顯示器玻璃基板的碎玻璃為原料的鹼石灰硼 酸鹽類短纖維玻璃配料，，，在上述技術中，作為短纖維玻璃 的必要成分的b2o3和ai2o3的供應原料，使用無鹼鋁硼矽酸 鹽類顯示碎玻璃，從而獲得經濟性高的配料。 作為太陽能電池用鹼石灰矽酸鹽類玻璃的現有技術’ 有大韓民國公開專利10-2009-0132742號的“具有高透過率 的無色鹼石灰玻璃成分”，在上述技術中，為了獲得高的可 視光線透過率，除含有0.01〜0.05重量份的Fe203之外，還 含有0,01〜0.3重量份的Μη02，但與無鹼鋁硼矽酸鹽類顯示 碎玻璃的回收利用無關。 另外，作為太陽能電池用鹼石灰矽酸鹽類玻璃的現有 技術，有PCT WO 2007/106223 A1的“低鐵高透過率太陽能 電池用浮法玻璃及其製造方法（Low Irion High Transmission Float Glass for Solar Cell Application and Method of Making Same)”，在上述技術中，製造不含Al2〇3， 而含0.001〜0.1重量份的Fe203的鹼石灰矽酸鹽類玻璃成 分，但與無鹼鋁硼矽酸鹽類顯示碎玻璃的應用無關。 另外，作為太陽能電池用玻璃的相關技術’有日本公 開專利2008-280189號的“太陽能電池用玻璃基板及其製造 方法’’，在上述技術中，在Si02、Al2〇3、Na2〇、K20的成分 範圍方面，與現有的鹼石灰矽酸鹽類玻璃具有完全不同的 玻璃成分。 201213267 如上所述’對於在纖維玻螭製造過程中，回收利用無 鹼鋁硼矽酸鹽類薄膜電晶體液晶顯示器玻璃基板的碎玻璃 的專利，如在本發明_那樣’將無鹼鋁硼矽酸鹽類顯示碎 玻璃加入用於製造太陽能電池用低鐵驗石灰石夕酸鹽類平板 玻璃的配料成分，以製造具有低廉的製造成本和高品質的 平板玻璃的方法及其配料，因可積極培育無鹼銘硼矽酸鹽 類顯示碎玻璃的回收利用領域，從而具有重大意義。 t ^^明内容】 發明概要 本發明的目的在於克服現有技術之不足而提供一種玻 璃配料，其將作為太陽能電池用低鐵驗石灰石夕酸鹽類平板 玻璃的製造原料的矽砂或矽石、石灰石、白雲石或菱鎮石、 氧化銘或氫氧化铭等的部份或全部用無驗銘硼石夕酸鹽類顯 示碎玻璃替代，但上述平板玻璃的物理化學性質、品質至 少不會受影響，甚至得到改善。 本發明的另一目的在於，提供一種玻璃配料，其雖然 使用無鹼鋁硼矽酸鹽類顯示碎玻璃，但可最大限度地保留 先前太陽能電池用平板玻璃製造工藝及工藝變數，因此無 需為新成分增加新工藝或增設新生產線，從而其經濟性非 常好。 本發明的又一目的在於，提供一種玻璃配料，其可直 接回收利用廢棄的無鹼鋁硼矽酸鹽類顯示碎玻璃，從而節 省原料費用，降低製造成本。 本發明的還一目的在於，在玻璃的製造工藝中，將難 6 201213267 相無需特殊管理的替代原料無㈣•夕 管示碎玻璃替代，從而消除原料的…^ 達到簡化的，難^略早獨管理原料所需的額外設備，以 匕工藝，提面工藝經濟性。 ^了達到上i4目的’本發明以無⑽卿 碎玻璃為原料的太陽能電池用彳貝不 用低鐵平板玻魏料，在太陽 4池用低麟石灰錢鹽類平板 ^ 料中的矽砂、矽石或矽石，丨、夺Λ 以上述配 口主6 彳或夕·"和石夕石的混合物作為100重量份 時，包含32〜36重量份的蔽扣允_ c f 3 ’、 T A、0.5〜h5重量份的芒硝、 ^〜24重1份的錢_錢鹽_科_、從 菱鎂石及白雲石中選擇的一種。 、 較佳地，在以上述石夕砂、石夕石或石夕砂和石夕石的混合物 作為⑽重量份時’上述石灰石包含21〜22重量份上述菱 鎖石包含5〜6重量份。 較佳地，在以上述石夕砂、石夕石或石夕砂和石夕石的混合物 作為⑽重量份時，上述石灰石包含7〜9重量份，上述白雲 石包含23〜27重量份。 在通過炼融上述太陽能電池用低鐵驗石灰砂酸鹽類平 板玻璃配料製造而成的平板破璃中，在以上述平板玻璃作 為100重量份時’包含7G〜75重量份的聊、⑽13〜讀8 重量份的Fe2〇3、〇·5〜2重量份的Al2〇3、〇 μ作量份的 Β2〇3 ' 12〜14重量份的Na2〇及Κ2〇、1〇〜13重量份的 MgO、CaO、SrO及BaO、〇.〇1 〜i 重量份的 Sr〇。 如上所述，本發明提供將太陽能電池用低鐵驗石灰石夕 7 201213267 酸鹽類平板玻璃的製造原料的一部份用無驗鋁棚矽酸鹽類 顯示碎玻璃替代，但不破壞玻璃的製造工藝和物理化學性 質，甚至得到改善的配料，從而降低玻璃的製造成本，減 少因廢棄或掩埋無鹼鋁硼矽酸鹽類顯示碎玻璃所產生的環 境負擔。 即’在有限的範圍内增加無鹼鋁硼矽酸鹽類顯示碎玻 璃的重量份的配料中，矽砂、石灰石、白雲石或菱鎂石及 氧化鋁的一部份或全部被無鹼鋁硼矽酸鹽類顯示碎玻璃替 代，從而不僅提高由配料製造而成的玻璃的悟性，而且， 還通過減少配料的熔融及澄清所需的能源，排除失透 (devitrification)等，大幅降低玻璃的製造成本。與此同時， 使用雜質Fe2〇3的濃度非常低，含有B2〇3且具有優秀的均句 性的碎玻璃，而且，因而提高了平板玻璃的功能，因此， 可增加太陽光線的透過率，増加化學财久性。 尤其疋’含有Fe2〇3等雜質的原料需經過非常嚴格的精 練過程絲雜f，但若使用祕纟S硼⑪酸鹽類顯示碎玻 璃’則無需上述過卿可防止雜質混人太陽能電池用平板 玻璃。 另外’因構成配料的原料或成分的相當—部份被碎 璃替代，因此’可消除原料的供應、管理、保管及投入 程中所產线大部制題，從而福上非常有利。 I：實施方式3 較佳實施例之詳細說明 下面，結合較佳實施例對本發明進行詳細說明。 8 201213267 在用無鹼鋁硼矽酸鹽類顯示碎玻璃製造鹼石灰矽酸鹽 類太陽能電池用平板玻璃時，將一併添加B2〇3成分，而在 不改變太陽能電池用平板破璃物性的範圍内少量添加的 B203 ’與原來存在的Al2〇3成分一樣，限制包含於玻璃中的 Na20及K2〇4驗性成分，有助於大幅提高太陽能 電池玻璃 的耐候性(對雨、雪、濕氣等的耐侵蝕性）。 但是，在現有技術的製造平板玻璃的過程中，若為了 供應秘一使时為單獨供應原料硼酸或辦，則存在如 下問題： 1) 因坞〇3具有吸濕性，對濕氣較脆弱，因此，濕氣對 上述原料的管理及保管影響較大； 2) 在製造平板玻璃的溶融過程中，上述原料飛滅以粒 子狀態排出至外部而污染大氣； 3) 上述原料在玻駐業用原料中屬於價格报高的原料。 因此，如本發明那樣，若在製造太陽能電池用平板玻 填的製造過程中使用無驗㈣石夕酸鹽類顯示碎玻璃，則無 需單獨保管或管理B2〇3工業原料，而且，因已通過熔融使 B2〇3作為成分存在於平板玻璃内部，因此，在將碎玻璃作 為原料使用時無B2〇3飛濺的危險，另外，無需為供應B2〇3 而耗費額外的費用。 因此’較之在製造太陽能電池用平板玻璃過程中單獨 使用b2〇3，作為B2〇3的供應源使用碎玻璃原料的方法，在 工藝上及卫藝成本上非常有利，而這就是本發明的特點。 另外，在鹼石灰矽酸鹽類太陽能電池用玻璃的情況 201213267 下’為了提高光電效率而在400〜llOOnm的範圍之内，將太 陽光線透過率調節至90%以上，但若在上述太陽能電池用 玻璃中以雜質混入的Fe2〇3的含量高於全部玻璃重量的〇 〇2 重量份(200ppm)，則太陽光線透過率將降低至90%以下，因 此，在太陽能電池玻璃的情況下，需將FesO3的含量調節至 0.02重量份(200ppm)以下。 因此，需最大限度地減少Fe2〇3的含量，但為了去除 FqO3需要粉碎及脫鐵等精練過程’從而增加工藝複雜性。 但是，本發明的顯示玻璃，因FqO3的含量已調節成相對於 全部玻璃重量的0.015重量份（i5〇ppm)〜0 02重量份 (200PPm)的範圍，因此，利用上述原料製造太陽能電池用 玻璃，無需擔心降低鹼石灰矽酸鹽類太陽能電池玻璃原來 的太陽光線透過率。 因此，本發明的特徵在於，利用顯示碎玻璃容易製造 減少Fe2〇3雜質含量的高品質的太陽能電池用玻璃，而且， 無需Fe2〇3等雜質的精煉等其他的過程。 本發明較佳實施例的太陽能電池用低鐵驗石灰石夕酸晓 類玻璃配料，相對於_重量份的作為Si〇2的供應原料的石: 砂或石夕石’包括32〜364量㈣作為叫⑽供應原料的蘇 打灰、21〜22重量份的作為⑽的供應原料的石灰石、％ 6重量份的作為Mg0的供應原料的菱鎂石5〜6重量份、〇.5 〜1.5重量份的作為料_芒_娜4)'3〜24重量份的 無驗銘硼料聽顯㈣玻璃，而若分⑽融上述配料製 作而成的玻璃的化學成分，則包括7()〜75重量份的 10 201213267 0.013〜〇·018重量份的Fe2〇3、〇 5〜2重量份的从〇3、〇卜 1.3重量份的Β203、12〜14重量份的Na2◦及κ2〇、1〇〜13重 量份的MgO、CaO、⑽及祕、〇⑴叫重量份的⑽。 在此，B2〇3包括〇」〜！ 3重量份，若上述B2〇3少於作為 下限值的0.1重量份，則对候性增加減彡，而若高於作為上 限值的1.3重量份，則將改變平板玻璃的物性，影響品質， 因此，B2Q3在上述範圍之内具有其臨界性意^具體而言， 若高於作為上述上限值的h3重量份，則耗會增加對水的 耐侵蝕性，但在與太陽能電池用玻璃的生產相關的其他物 性，例如，玻璃黏度、軟化點等發生很到的變化，而且， 大大改變玻璃自身的熱膨脹係數。即，因給太陽能電池用 平板玻璃的生產工藝和基本物性產生較大影響，ΙΑ的添 加量受限制，而1.3重量份就是限定值。 因此，有限使用含有ΙΟ3的顯示玻璃，具有增進太陽 能電池用玻璃的功能，簡化原料投入工藝等優點，因此， 其使用本身具有重要的意義，構成本發明的特點。 另外，在此所使用的無鹼鋁硼矽酸鹽類顯示碎玻璃’ 因其主要成分是Si〇2、ai2o3、鹼土(Mg0+Ca0+Sr〇+Ba〇) 及B2〇3，因此，可成為部份或全部替代作為&〇2的供應原 料的矽砂或矽石、作為Ca0的供應原料的石灰石和白雲 石、作為Al2〇3的供應原料的氧化鋁的原料，而且，無鹼鋁 硼矽酸鹽類顯示碎玻璃，因fqo3的含量很低，因此，可在 作為要求太陽光線高透過率的太陽能電池用低鐵平板玻璃 的原料方面有很高的利用價值，較之不使用上述碎玻璃而 11 201213267 只用原料製造平板玻璃的方法，因沒有從原料中去除Fe203 等雜質的嚴格的精煉過程，而使用已具有很低的？6203含量 的碎玻璃，從而非常有利於太陽能電池用低鐵平板玻璃的 製造。 另外’因構成配料的大部份原料都是結晶性固體，因 此，在熔融成液體的過程中消耗相當多的能源，但因無鹼 在呂糊石夕酸鹽類顯示碎玻璃是已具有液體結構的玻璃，從而 節省相當於替代結晶性原料的量的能源。 平板玻璃配料的熔融溫度是1500〜155CTC，熔融體經 過去泡的澄清工藝，在約104〜107 6poise的黏度的溫度範圍 内’成里為板狀。尤其是’為防止局部形成結晶的失透， 液體溫度需低於l〇4poise的作業溫度。與此同時，各玻璃具 有作為商品應具備的各種物理化學性質。 匕為最大限度地提高作為替代原料的無驗紹棚石夕 酸鹽類顯示碎玻璃的效果，在儘量維持平板玻璃的製造工 藝的範圍之内，選擇配料中無鹼鋁硼矽酸鹽類顯示碎玻璃 所、適田的量，以維持或敢刪物理化學性質，而上述適 當0L里疋在以配料巾的卿、料或料㈣石的混合物 臺刀時，包括3〜24重量份的無驗鋁硼石夕酸鹽類顯 示碎破墻，％ y·，丄 在境樣的量化特性為基礎的平板玻璃的含量 _ 之內具有其臨界性意義。 > _而σ右無鹼鋁硼矽酸鹽類顯示碎玻璃少於上述3 =本=達代原料的效果，從而失去降低 我而右多於上述24重量份，則不僅導致製 12 201213267 造工藝的變化，而且，大幅改變玻璃的物理化學性質，從 而喪失原太陽能電池用玻璃的目的。 因此，在本發明中，考慮到低鐵鹼石灰矽酸鹽類平板 玻璃的成分，製造混合無鹼鋁硼矽酸鹽類顯示碎玻璃和其 他原料的各種配料，並调查炼融後製造的玻璃的特性，以 開發出維持或改善平板玻璃的製造工藝和物理化學性質的 配料。 用於本發明的無鹼鋁硼矽酸鹽類顯示碎玻璃是薄膜電 晶體液晶顯示器用基板玻璃的製造及加工工藝中產生的碎 玻璃，具有如[表1]所示的組成。下面的組成表示的是相對 於全部碎玻璃重量的相對重量。 [表1] 成分 重量份 Si〇2 58 〜64 Al2〇3 15〜18 B2〇3 7〜11 MgO 0〜4 CaO 3〜8 SrO 0.5 〜8 BaO 0〜3 Sn〇2 0 〜0.5 ZnO 0 〜0.5 Sb2〇3 0 〜0.5 AS2〇3 0 〜0.8 Fe2〇3 0.015 〜0.02 另外，對被無鹼鋁硼矽酸鹽類顯示碎玻璃替代的各主 要成分的作用及優點說明如下：201213267 VI. Description of the invention: [Picture of the invention] The present invention relates to a commercial production process of a low-iron alkali-free aluminum boron bismuth silicate glass to be used for a thin film transistor liquid crystal display. The cullet produced in the recycling is a raw material of a soda-lime-silicate solar cell substrate or a flat glass for a cover, and maintains or improves the manufacturing process and physicochemical properties of the glass. C prior art 3 BACKGROUND OF THE INVENTION Broken glass can be defined as poor glass, glass that cannot be used due to breakage, glass) or broken glass of βσ, which is inevitably produced in the manufacture and processing of glass or glass products. In the glass industry, cullet is generally considered to be strictly managed as a material that can be recycled. In particular, the alkali-free aluminum boron phthalate display glass used for the thin film transistor liquid crystal display has the function of protecting the core components of the display and transmitting images, so that it cannot produce even a small defect rate, compared with ordinary window glass or Food glass, its manufacturing process or quality control is very strict. Therefore, in the manufacturing and processing of the substrate glass, if dissolution failure, appearance defects, and dimensional defects occur, it is necessary to discard these as defective products, and a large amount of broken glass is generated in the process. However, in order to continuously maintain the quality as the display glass, once the defective display glass is broken, it will no longer be used to display the glass manufacturing process, and the waste glass will be subjected to flooding treatment, etc., and the amount thereof is large. The alkali-free aluminum borosilicate type display glass is completely free of alkali in terms of composition, and the content of Fe203 which exists as an impurity in 201213267 has a range value of 0.015 parts by weight (150 ppm) to 〇·〇2 parts by weight (200 ppm). Therefore, the content is very low, and if SiO 2 , Al 2 〇 3 , alkaline earth (MgO + CaO + SrO + BaO) and B 2 〇 3 are the main components, since these components can be sufficiently mixed by the melting process, the uniformity is high. Premium glass. In addition, the solar cell glass is a lime-silicate glass, which can be used for a substrate or a cover depending on the type of the solar cell, and SiO 2 , CaO 'MgO, Na20 are main components, and in order to increase the glass which affects the photoelectric efficiency of the solar cell. The solar light transmittance is limited to the content of Fe203 as an impurity below 2 parts by weight (200 ppm), and in consideration of the rain, snow or atmospheric moisture which affects the erosion of the glass surface, Alz〇3 The content is adjusted to about 1 to 2 parts by weight to improve weather resistance. Therefore, the above-mentioned low-iron display glass can be a part of the raw material required for the manufacture of low-iron lime-calcium silicate solar cell glass by adjusting an appropriate amount, that is, the composition of the ingredients. There is a growing interest in the recycling of un-tested borates to show broken glass. Therefore, it is necessary to continue to develop methods and fields for recycling waste glass without recycling. As a prior art for recycling smashed glass using alkali-free aluminum borosilicate, "a smashed glass of a glass substrate of a thin film electro-crystal hybrid crystal display" is used as a raw material. The invention relates to a method for recycling broken glass in a manufacturing process of a substrate for a liquid crystal display, which is characterized in that the ingredient contains an alkali-free aluminum boron borate-based display cullet, But it has nothing to do with the application of low-iron solar cells. 201213267 In addition, as a prior art for recycling smashed glass using alkali-free aluminum borosilicate, there is a soda lime borate based on cullet of a thin film transistor liquid crystal display glass substrate, which is incorporated in Korean Patent No. 10-0929869. Short-fiber glass-based ingredients, in the above-mentioned technology, b2o3 and ai2o3, which are essential components of short-fiber glass, use an alkali-free aluminum boron silicate to display cullet, thereby obtaining an economical high-yield ingredient. A prior art of a soda lime silicate glass for a solar cell, "a colorless soda lime glass component having a high transmittance" in the above-mentioned technique, in order to obtain high visible light transmission. In addition to 0.01 to 0.05 parts by weight of Fe203, it also contains 0,01 to 0.3 parts by weight of Μη02, but it is not related to the recovery of ash glass by the alkali-free aluminum borosilicate. The prior art of soda lime silicate glass has the "low iron high transmittance solar cell float glass" of PCT WO 2007/106223 A1 (Low Irion High Transmission Float Glass for Solar Cell Application and Method of Making Same), in the above technique, a soda lime citrate containing no Al 2 〇 3 and containing 0.001 to 0.1 parts by weight of Fe 203 is produced. Glass-like component, but it is not related to the application of the alkali-free aluminum borosilicate-based cullet. In addition, as a related art of the glass for solar cells, there is a "glass substrate for solar cell and its manufacture" of Japanese Laid-Open Patent Publication No. 2008-280189 The method '', in the above technique, has a completely different glass component from the conventional soda lime silicate glass in terms of the composition range of SiO 2 , Al 2 〇 3 , Na 2 〇, and K 20 . 201213267 As described above, 'the patent for recycling cullet of an alkali-free aluminum borosilicate-based thin film transistor liquid crystal display glass substrate in the fiberglass manufacturing process, as in the present invention _ will be an alkali-free aluminum boron lanthanum The acid salt shows that the cullet is added to the ingredients for the manufacture of the low-iron limestone silicate flat glass for solar cells, and the method and the ingredients thereof for manufacturing the flat glass with low manufacturing cost and high quality are actively cultivated. The alkali-free borates are of great significance in the field of recycling of broken glass. SUMMARY OF THE INVENTION The present invention aims to overcome the deficiencies of the prior art and to provide a glass batch which will be used as a raw material for the production of low-iron limestone lime-like flat glass for solar cells. Some or all of limestone, dolomite or lingzhen stone, oxidized or oxidized, etc. are replaced by cullet, which is not subject to physicochemical properties and quality. The impact has even improved. Another object of the present invention is to provide a glass batching material which exhibits cullet using an alkali-free aluminum boron borate, but which can retain the manufacturing process and process variables of the previous flat glass for solar cells to the utmost extent, and therefore need not be new The addition of new processes or the addition of new production lines makes the economy very good. It is still another object of the present invention to provide a glass batch which can directly recycle waste glass using waste alkali-free aluminum boron silicate, thereby saving material costs and reducing manufacturing costs. A further object of the present invention is that in the manufacturing process of the glass, it is difficult to replace the raw materials without special management, and the replacement of the raw materials is eliminated by the replacement of the raw materials. The additional equipment required for the management of raw materials, in order to process the process and economical. ^To achieve the purpose of i4] The present invention uses no (10) smashed glass as the raw material for the solar cell mussels without the use of low-iron flat glass, and in the solar 4 pool with low-lime lime money and salt flats, Meteorite or vermiculite, 丨, Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ 0.5 to h5 parts by weight of Glauber's salt, ^~24 weight 1 part of money _ money salt _ _, one selected from magnesite and dolomite. Preferably, when the mixture of the above-mentioned Shi Xi sand, Shi Xi stone or Shi Xi sand and Shi Xi stone is (10) parts by weight, the limestone contains 21 to 22 parts by weight of the above-mentioned rhombohedron and 5 to 6 parts by weight. Preferably, when the mixture of the above-mentioned Shixia sand, Shi Xishi or Shi Xi sand and Shi Xi stone is (10) parts by weight, the limestone contains 7 to 9 parts by weight, and the dolomite contains 23 to 27 parts by weight. In the flat glass granules produced by the smelting of the low-iron shale-lime sulphate-type flat glass granules for the above-mentioned solar cells, when the flat glass is used as 100 parts by weight, 'containing 7G to 75 parts by weight of chat, (10) 13~ 8 parts by weight of Fe2〇3, 〇·5~2 parts by weight of Al2〇3, 〇μ parts of Β2〇3' 12~14 parts by weight of Na2〇 and Κ2〇, 1〇~13 parts by weight MgO, CaO, SrO, and BaO, 〇.〇1 to i parts by weight of Sr〇. As described above, the present invention provides a part of the raw material for manufacturing a solar cell low-iron limestone limestone 7 201213267 acid plate glass, which is replaced by a non-aluminum shed silicate display cullet, but does not destroy the glass. Process and physicochemical properties, even improved ingredients, thereby reducing the cost of glass manufacturing and reducing the environmental burden of culminating glass by the disposal or burying of alkali-free aluminum boron bismuth silicates. That is, in a limited range of addition of alkali-free aluminum boron borates to the weight fraction of the cullet, some or all of the strontium sand, limestone, dolomite or magnesite and alumina are alkali-free aluminum. Borosilicates show the replacement of broken glass, which not only improves the understanding of the glass made from the ingredients, but also reduces the devitrification, etc., by reducing the energy required for melting and clarifying the ingredients, and greatly reducing the glass. manufacturing cost. At the same time, the use of the impurity Fe2〇3 is very low, and contains B2〇3 and has excellent uniformity of broken glass, and thus, the function of the flat glass is improved, so that the transmittance of the solar light can be increased. Chemical longevity. In particular, raw materials containing impurities such as Fe2〇3 undergo a very strict scouring process, but if the use of the secret S boron 11 acid salt shows broken glass, it is not necessary to prevent the impurities from being mixed with solar cells. plate glass. In addition, because the raw materials or components constituting the ingredients are partially replaced by broken glass, it is very advantageous to eliminate the supply, management, storage, and production of the raw materials in the production process. I. Embodiment 3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail in conjunction with preferred embodiments. 8 201213267 When the smashed glass is used to produce the smashed glass for the soda lime silicate solar cell, the B2 〇 3 component is added together without changing the physical properties of the solar cell slab. A small amount of B203' added in the range, like the original Al2〇3 component, limits the Na20 and K2〇4 intrinsic components contained in the glass, which helps to greatly improve the weather resistance of solar cell glass (for rain, snow, and wet). Corrosion resistance of gas, etc.). However, in the prior art process of manufacturing flat glass, if the raw material boric acid is supplied separately for the purpose of supplying the secret, the following problems exist: 1) Since the dock 3 is hygroscopic, it is weak to moisture, Therefore, moisture has a great influence on the management and storage of the above raw materials; 2) in the process of manufacturing the flat glass, the raw materials are flung out and discharged to the outside in the form of particles to pollute the atmosphere; 3) the raw materials for the above-mentioned raw materials in glass It is a raw material with a high price. Therefore, as in the present invention, if the cullet is used in the manufacturing process for manufacturing the flat glass filler for solar cells, it is not necessary to separately store or manage the B2〇3 industrial raw materials, and The melting causes B2〇3 to exist as a component inside the flat glass. Therefore, there is no risk of B2〇3 splashing when the cullet is used as a raw material, and it is not necessary to charge B2〇3 for additional cost. Therefore, the method of using cullet raw material as a supply source of B2〇3 is very advantageous in terms of process and the cost of the art, compared to the use of b2〇3 in the process of manufacturing flat glass for solar cells, and this is the advantage of the present invention. Features. In addition, in the case of the glass for the soda lime silicate-based solar cell, the solar light transmittance is adjusted to 90% or more in the range of 400 to 100 nm in order to improve the photoelectric efficiency, but the solar cell is used for the above solar cell. When the content of Fe2〇3 mixed with impurities in the glass is higher than 〇〇2 parts by weight (200 ppm) of the total weight of the glass, the solar light transmittance is reduced to 90% or less. Therefore, in the case of solar cell glass, it is necessary to The content of FesO3 was adjusted to 0.02 part by weight (200 ppm) or less. Therefore, it is necessary to minimize the content of Fe2〇3, but in order to remove FqO3, a scouring process such as pulverization and de-ironing is required to increase the process complexity. However, in the display glass of the present invention, since the content of FqO3 is adjusted to be in the range of 0.015 parts by weight (i5 〇 ppm) to 0.02 parts by weight (200 ppm) based on the total weight of the glass, the glass for solar cells is produced from the above raw materials. There is no need to worry about lowering the original solar light transmittance of soda lime tantalate solar cell glass. Therefore, the present invention is characterized in that it is easy to produce a high-quality solar cell glass which reduces the impurity content of Fe2〇3 by using cullet, and further processes such as refining of impurities such as Fe2〇3 are not required. In the solar cell of the preferred embodiment of the present invention, the low-iron limestone lime-based glass-based material is used as a raw material for the supply of Si〇2 with respect to _ parts by weight of the stone: sand or Shishishi' includes 32 to 364 (four) as (10) Soda ash for supplying raw materials, 21 to 22 parts by weight of limestone as a raw material for supply of (10), and 6 parts by weight of magnesite as a raw material for supply of Mg0, 5 to 6 parts by weight, 〇.5 to 1.5 parts by weight As the material _ _ _ Na 4) '3 ~ 24 parts by weight of the non-examination of the boron material to listen to (four) glass, and if the chemical composition of the glass produced by the above ingredients (10), including 7 () ~ 75 parts by weight 10 201213267 0.013~〇·018 parts by weight of Fe2〇3, 〇5~2 parts by weight of 〇3, 1.3Bu 1.3 parts by weight of Β203, 12-14 parts by weight of Na2◦ and κ2〇, 1〇~13 Parts by weight of MgO, CaO, (10) and secret, 〇 (1) are called parts by weight (10). Here, B2〇3 includes 〇"~! 3 parts by weight, if the above B2〇3 is less than 0.1 part by weight as the lower limit value, the increase in the valence is reduced, and if it is higher than the upper limit of 1.3 parts by weight, the physical properties of the flat glass are changed, and the influence is affected. Quality, therefore, B2Q3 has its criticality within the above range. Specifically, if it is higher than h3 by weight as the above upper limit, the consumption of water is increased, but it is used for solar cells. Other physical properties related to the production of glass, such as glass viscosity, softening point, etc., are very variable, and the thermal expansion coefficient of the glass itself is greatly changed. Namely, since the production process and basic physical properties of the flat glass for solar cells are greatly affected, the amount of niobium added is limited, and 1.3 parts by weight is a limit value. Therefore, the limited use of the display glass containing ruthenium 3 has the advantages of improving the function of the solar cell battery and simplifying the raw material input process. Therefore, the use itself has an important meaning and constitutes a feature of the present invention. In addition, the alkali-free aluminum boron bismuth silicate used herein shows cullet ' because its main components are Si 〇 2, ai 2 o 3 , alkaline earth (Mg0+Ca0+Sr〇+Ba〇) and B2〇3, therefore, It is a raw material that partially or completely replaces cerium or vermiculite which is a raw material for supply of & 〇2, limestone and dolomite which are raw materials for supply of Ca0, alumina which is a raw material for supply of Al2〇3, and alkali-free aluminum Borosilicates show cullet, because the content of fqo3 is very low, so it can be used as a raw material for low-iron flat glass for solar cells requiring high transmittance of solar light, compared to the above. Broken glass and 11 201213267 The method of making flat glass only from raw materials, because there is no strict refining process to remove impurities such as Fe203 from raw materials, and the use has been very low? 6203 content of broken glass, which is very beneficial to the manufacture of low-iron flat glass for solar cells. In addition, because most of the raw materials that make up the ingredients are crystalline solids, a considerable amount of energy is consumed in the process of melting into liquids, but because of the alkali-free, it is shown that the broken glass has liquid. The structure of the glass, thereby saving energy equivalent to the amount of crystalline raw materials. The melting temperature of the flat glass ingot is 1500 to 155 CTC, and the melt is clarified by the past bubble, and is in the form of a plate in a temperature range of about 104 to 107 6 poise. In particular, to prevent devitrification of locally formed crystals, the liquid temperature needs to be lower than the operating temperature of l〇4poise. At the same time, each glass has various physical and chemical properties as a product.最大限度In order to maximize the effect of the sinter glass as a substitute raw material, the alkali-free aluminum boron silicate display in the batch is selected within the range of manufacturing process of the flat glass as much as possible. The amount of cullet, the amount of the field, to maintain or dare to delete the physicochemical properties, and the above appropriate 0L in the mixture of the ingredients of the ingredients, materials or materials (four) stone, including 3 to 24 parts by weight The aluminum borax compound shows a broken wall, and % y·, 丄 has a critical significance within the content of the flat glass based on the quantitative properties of the environment. > _ and σ right alkali-free aluminum boron bismuth citrate shows that the cullet is less than the above 3 = this = the effect of the raw materials, thus losing the reduction and the right more than the above 24 parts by weight, not only led to the creation of 12 201213267 The process changes, and, in addition, greatly changes the physicochemical properties of the glass, thereby losing the purpose of the original solar cell glass. Therefore, in the present invention, in consideration of the composition of the low-iron-alkali lime silicate-type flat glass, various ingredients for mixing the alkali-free aluminum borosilicate exhibiting cullet and other raw materials are produced, and the glass produced after the smelting is investigated. Characteristics to develop ingredients that maintain or improve the manufacturing process and physicochemical properties of flat glass. The alkali-free aluminum borosilicate type used in the present invention shows that cullet is a cullet produced in the production and processing of a substrate glass for a thin film transistor liquid crystal display, and has a composition as shown in [Table 1]. The following composition shows the relative weight relative to the weight of all cullet. [Table 1] Component parts by weight Si〇2 58 to 64 Al2〇3 15~18 B2〇3 7~11 MgO 0~4 CaO 3~8 SrO 0.5 〜8 BaO 0~3 Sn〇2 0 ～0.5 ZnO 0 〜 0.5 Sb2〇3 0 to 0.5 AS2〇3 0 to 0.8 Fe2〇3 0.015 to 0.02 In addition, the effects and advantages of the main components replaced by the alkali-free aluminum boron borates are shown as follows:
Si02為參與玻璃成型的必需氧化物，是穩定玻璃網狀 結構的成分。若作為Si02的供應原料的結晶質矽石或矽砂 13 201213267 的一部份被無鹼鋁硼矽酸鹽類顯示碎玻螭替代，則因增加 配料的熔融性，從而節省製造玻璃時所需的能源。 另外，Al2〇3是作為抑制玻璃的失透並增進化學耐久性 的成分所添加的，而若作為Al2〇3的供應原料的結晶質氧化 鋁的部份或全部被無鹼鋁硼矽酸鹽類顯示碎玻璃替代，則 因增加配料的熔融性而具有節省能源的效果，而且，大幅 節省成本。 另外，B2〇2為與Si〇2—道參與玻璃成型的氧化物，促 進配料的熔融，減少玻璃的熱膨脹係數，提高軟化點並增 進化學耐久性。若將無鹼鋁硼矽酸鹽類顯示碎玻璃用作平 板玻璃的原料，則因含有微量的ΙΑ成分，從而提高玻璃 的化學耐久性和耐候性。 另外，MgO、CaO、SrO及BaO在促進配料的熔融的同 時，在高溫下降低玻璃的黏度，且在低溫下提高玻璃的黏 度。若作為雜質含有FqO3的MgO和CaO的結晶性供應原料 的一部份被無鹼鋁硼矽酸鹽類顯示碎玻璃替代，則可増加 配料的熔融性和玻璃產品的太陽光線透過率，而同時所含 有的SrO和BaO因其含量何地，幾乎不對玻璃的特性產生影響。 本發明的配料包含供應上述成分的無鹼鋁硼石夕酸鹽類 顯示碎玻璃’從而維持或改善太陽能電池用平板玻轉的各 種特性。此時，各種特性是指，在平板玻璃的生產方面 對lOOpoise的澄清溫度為1450°C以下，對l〇,000poise的作業 溫度為1030°C以下，液體溫度為1010°C以下，作業溫声和 液體溫度之差為25°C以上’液體溫度下的黏度值為 14 201213267 15000poise以上’而在玻璃產品方面’在400〜1 i〇〇nm的波 長範圍，4mm厚度的太陽光線透過率為90%以上，熱膨脹 係數為91xlO_7/°C以下，而作為化學耐久性指標的鹼溶出度 為0.25mg/g以下。 [實施例] 根據如下[表2]的配料比率稱重混合各原料並獲得總重 量為500g的配料之後，利用700cc的翻金掛禍，在1550°C的 溫度條件下熔融3小時，接著，利用鉑金攪拌器進行均質處 理並成型為板狀之後，利用電爐，在550°C的溫度條件下維 持2小時，接著，直至溫度達到350°C為止，每分鐘降低5。(3 的溫度’緩冷製造玻璃。 對於各配料的熔融性，及以所製造的各玻璃為物件， 測量高溫黏度、液體溫度、軟化點、熱膨脹係數、鹼溶出 度及可視光線透過率，且將其結果示於[表2]的下端。在[表 2]中’配料熔融性(。〇是指，在900〜1300t的溫度範圍， 將各配料維持4小時之後，結晶小時的溫度；Tm指對1 〇〇p〇ise 的溫度’而1^指對開始成形的l〇,〇〇〇p〇ise的溫度。另外， TliC)指發生失透的液體溫度，而在液體溫度的黏度值(atTiiq) 使利用它溫度關係式l〇gT1=A+B/(T-T。)計算出來的。在此，η 為年度，A、Β及Τ。為常數，Τ為溫度(。〇。另外，ΛΤ只成 型溫度和液體溫度之差（Tw-Tliq)，α指25〜50(TC之間的熱膨 脹係數’ Tvis指在4〇〇〜ii〇〇nm範圍的，4mm厚度的太陽光 線透過率。 15 201213267 [表2] __h 氧料及特性 實施例 比j 交例 1 2 3 4 1 2 穸石 100 100 100 100 100 100 重 蘇打灰 33.2 34.1 35.1 35.8 33.0 34 衫石 21.8 21.8 21.8 21.8 21.8 22.1 量 菱鎂石 5.4 5.5 5.5 5.6 5.3 5.5 份 氧化銘 ---- 0 0 0 0 0.5 0.3 _芒確 0.9 0.9 0.9 0.9 0.8 0.9 無鹼鋁硼矽酸鹽 類顯示碎玻璃 4.2 8.7 13.4 16.7 0 0 _熔融性 1100 1070 1050 1030 1100 1100 Tm( C ) 1435 1433 1435 1438 1435 1437 TW(°C ) 1019 1018 1020 1020 1019 1021 Tliq( C ) 985 986 982 978 988 984 特 Π at Tnq(p〇ise) 19764 18960 17485 16982 19952 20045 性 ΔΤ(°〇 34 32 38 42 31 37 軟化點（°C) 721 722 722 724 720 722 A(xl〇-v/°C ) 90.0 89.3 88.4 86.6 89.3 89.5 “溶出度 (mg/g) 0.20 0.20 0.17 0.13 0.23 0.23 Tvis(%) 91.1 91.1 91.2 91.3 90.7 90.5 上述[表2]的比較例是低鐵平板玻璃的商業配料，實施 例卜4是相對於1〇〇重量份的si〇2，包括4.2~16.7重量份的無 鹼鋁硼矽酸鹽類顯示碎玻璃的配料。從實施例可知，隨著 無鹼鋁硼矽酸鹽類顯示碎玻璃德重量份的增加，成為蘇打 灰、石灰石及菱鎂石的重量份發生細微的變化，但無需氧 化鋁的配料。 關於[表2]的特性部份，相對於上述各配料的玻璃特 性，可通過比較實施例和比較例總結如下： 1、在實施例中，結晶從配料完全消失的溫度（配料熔 融性的指標），較比較例最高低70°C，因此，隨著無鹼鋁硼 石夕酸鹽類顯示碎玻璃的重量份的增加’配料炼融性得到改 16 201213267 善。即，若添加碎玻璃，則可在低溫熔融，從而提高敏濟性。 2、 在實施例中，對iOOpoise的澄清溫度(Tm)和對1〇,0〇〇 的作業溫度(Tw)，大體上與比較例相同，因此，無需為酕 料的溶解及澄清對工藝進行改變。 3、 實施例的液體溫度(Tliq)較比較例最高低1〇<5(：左右， 各成分作業溫度和液體溫度之差（ΛΤ)為25°c以上，真在浪 體溫度的黏度值(η at Tliq)為15,〇〇〇p〇ise以上，從而具有％ 全排除失透的優秀的玻璃成型能力。 4、 實施例的軟化點在4°C的範圍内變化，而熱膨赚孫 數(α)反倒稍微減少，因此’會增加玻璃的耐熱衝擊,生。 5、 作為對水的玻璃的化學耐久性指標的實施例的鹼參 出度，因添加含有Β2〇3的無驗铭侧石夕酸鹽類顯示碎戒痛’ 較之比較例大幅減少，因此’增加長期露天使用的木皭能 電池用玻璃的對雨、雪或大氣中水分的耐候性，從而Α轉 增加太陽能電池的壽命。 6、 實施例的太陽光線透過率(Tvis)較比較例增加’從而 提高太陽能電池的光電效率。這與將要後述的Fe2〇3的含賣 有關，而若像實施例那樣使用無鹼鋁硼矽酸鹽類顯系碎破 璃，則無需其他的精煉過程，即可大幅降低作為雜質的 Fe203的量，因此’實施例的太陽光線透過率’較之比較糾 更高。 將利用上述[表2]的實施例和比較例的配料製造而成的 玻璃成分，以重量份表示為如下[表2]。比較[表3]的比較例 所示的只利用精煉的原料製造的成分和一併將無鹼鋁硼矽 17 S- 201213267 酸鹽類顯示碎玻璃作為原料的實施例的成分，則再本發明 實施例的情況下，Al2〇3稍微增加，而Fe2〇3較之從精煉的 工業原料混入的比較例的0.02重量份，在實施例的情況 下，隨著碎玻璃重量份的增加，大幅減少至0.015重量份， 而且，雖然混入B2〇3、SrO、Sn02的成分，但如[表2]的特 性所示，不僅不破壞玻璃原來的各種特性，至少維持或改 善玻璃的特性。 [表3] 實施例 比較例 成分 1 2 3 4 1 2 Si02 72.5 72.1 71.3 71.0 72.8 72.6 A】2〇3 0.57 1.0 1.5 1.9 0.4 0.18 B2O3 0.3 0.6 0.9 1.1 0 0 Na20 13.9 13.8 13.7 13.6 14 14 組成 (重量份） K20 0.1 0.1 0.1 0.1 0.1 0.1 MgO 3.9 3.8 3.8 3.8 3.9 3.6 CaO 8.6 8.5 8.5 8.4 8.7 9.5 SrO 0.02 0.04 0.07 0.08 0 0 Fe2〇3 0.018 0.0169 0.0153 0.0142 0.018 0.02 Sn02 0.01 0.02 0.03 0.04 0 0 上述實施例僅用以說明本發明而非限制，本領域的普 通技術人員應當理解，可以對本發明進行修改、變形或者 等同替換。而不脫離本發明的精神和範圍的，其均應涵蓋 在本發明的申請專利範圍當中。 【圖式簡單說明】 (無） 【主要元件符號說明】 (無） 18Si02 is an essential oxide involved in glass forming and is a component that stabilizes the glass network structure. If a part of the crystalline vermiculite or strontium sand 13 201213267, which is a raw material for the supply of SiO 2 , is replaced by an alkali-free aluminum borosilicate-based smashed glass crucible, the meltability of the ingredients is increased, thereby saving the need for manufacturing glass. Energy. Further, Al 2 〇 3 is added as a component which suppresses devitrification of the glass and enhances chemical durability, and if part or all of the crystalline alumina which is a raw material for supplying Al 2 〇 3 is alkali-free aluminum boron borate The class shows that the cullet replacement has an energy-saving effect by increasing the meltability of the ingredients, and the cost is greatly reduced. Further, B2〇2 is an oxide which participates in glass forming with Si〇2-channel, promotes melting of the ingredients, reduces the coefficient of thermal expansion of the glass, increases the softening point, and increases chemical durability. When the alkali-free aluminum boron borate-based cullet is used as a raw material for the flat glass, the chemical durability and weather resistance of the glass are improved by containing a trace amount of the cerium component. Further, MgO, CaO, SrO, and BaO promote the melting of the ingredients, lower the viscosity of the glass at a high temperature, and increase the viscosity of the glass at a low temperature. If a part of the crystalline raw material of MgO and CaO containing FqO3 as an impurity is replaced by an alkali-free aluminum boron silicate type cullet, the meltability of the ingredient and the solar light transmittance of the glass product can be added while The content of SrO and BaO contained therein hardly affects the characteristics of the glass due to its content. The furnish of the present invention comprises an alkali-free aluminosilicate which supplies the above-mentioned components to exhibit broken glass' to maintain or improve various characteristics of the glass transition of the solar cell. At this time, various characteristics mean that the clarification temperature of lOOpoise is less than 1450 ° C in the production of flat glass, the operating temperature of l〇, 000 poise is below 1030 ° C, the liquid temperature is below 1010 ° C, and the operation temperature is sound. The difference between the temperature of the liquid and the temperature of the liquid is 25 ° C or higher. The viscosity value at the liquid temperature is 14 201213267 15000 poise or more. In the glass product range, the solar light transmittance is 4 in the wavelength range of 400 to 1 i 〇〇 nm. Above 100%, the coefficient of thermal expansion is 91xlO_7/°C or less, and the alkali dissolution rate as an index of chemical durability is 0.25 mg/g or less. [Examples] After the respective raw materials were weighed and weighed according to the ratio of the ingredients of the following [Table 2] to obtain a total weight of 500 g, the mixture was melted at a temperature of 1,550 ° C for 3 hours by using a 700 cc gilt, and then, After homogenization treatment with a platinum stirrer and molding into a plate shape, it was maintained at a temperature of 550 ° C for 2 hours in an electric furnace, and then decreased to 5 per minute until the temperature reached 350 ° C. (3 temperature 'slow-cooled glass. For high-melness viscosity, liquid temperature, softening point, thermal expansion coefficient, alkali dissolution rate, and visible light transmittance, for each component's meltability, and for each of the manufactured glass materials, and The results are shown in the lower end of [Table 2]. In [Table 2], the formulation melting property (.〇 refers to the temperature at which the respective components are maintained for 4 hours in the temperature range of 900 to 1300 t, and the temperature of the crystallization is small; Tm Refers to the temperature of 1 〇〇p〇ise' and 1^ refers to the temperature of the 成形p〇ise which begins to form. In addition, TliC) refers to the temperature of the liquid which is devitrified and the viscosity at the liquid temperature. (atTiiq) is calculated using its temperature relation l〇gT1=A+B/(TT.), where η is the year, A, Β and Τ are constants, and Τ is the temperature (.〇. ΛΤ only the difference between the molding temperature and the liquid temperature (Tw-Tliq), α means 25~50 (the coefficient of thermal expansion between TC' Tvis refers to the solar light transmittance of 4mm thickness in the range of 4〇〇~ii〇〇nm. 15 201213267 [Table 2] __h Oxygen and characteristics examples than j Example 1 2 3 4 1 2 Meteorite 100 100 100 100 10 0 100 heavy soda ash 33.2 34.1 35.1 35.8 33.0 34 sill stone 21.8 21.8 21.8 21.8 21.8 22.1 amount of magnesite 5.4 5.5 5.5 5.6 5.3 5.5 parts oxidation Ming---- 0 0 0 0 0.5 0.3 _ Mang indeed 0.9 0.9 0.9 0.9 0.8 0.9 alkali-free aluminum boron silicates show broken glass 4.2 8.7 13.4 16.7 0 0 _ meltability 1100 1070 1050 1030 1100 1100 Tm ( C ) 1435 1433 1435 1438 1435 1437 TW (°C ) 1019 1018 1020 1020 1019 1021 Tliq ( C) 985 986 982 978 988 984 Features at Tnq(p〇ise) 19764 18960 17485 16982 19952 20045 Sex ΔΤ (°〇34 32 38 42 31 37 Softening point (°C) 721 722 722 724 720 722 A(xl〇 -v/°C ) 90.0 89.3 88.4 86.6 89.3 89.5 "Dissolution (mg/g) 0.20 0.20 0.17 0.13 0.23 0.23 Tvis (%) 91.1 91.1 91.2 91.3 90.7 90.5 The comparative example of [Table 2] above is low-iron flat glass Commercial Ingredients, Example 4 is a formulation showing cullet with respect to 1 part by weight of si〇2, including 4.2 to 16.7 parts by weight of alkali-free aluminum boron silicate. As apparent from the examples, as the alkali-free aluminum boron borates showed an increase in the weight fraction of broken glass, the weight fraction of soda ash, limestone and magnesite was slightly changed, but the aluminum oxide was not required. Regarding the characteristic portions of [Table 2], the glass characteristics of the above respective ingredients can be summarized as follows by comparative examples and comparative examples: 1. In the examples, the temperature at which the crystallization completely disappears from the ingredients (indicator of the meltability of the ingredients) ), the highest temperature is 70 ° C lower than the comparative example. Therefore, as the alkali-free aluminosilicate exhibits an increase in the weight fraction of the cullet, the ingredient smelting property is changed to 16 201213267. That is, when cullet is added, it can be melted at a low temperature, thereby improving sensitivity. 2. In the examples, the clarification temperature (Tm) for iOOpoise and the operating temperature (Tw) for 1 〇, 0 , are substantially the same as in the comparative example, so that the process does not need to be dissolved and clarified for the mash. change. 3. The liquid temperature (Tliq) of the example is lower than the comparative example by 1 〇 < 5 (: about, the difference between the operating temperature of each component and the liquid temperature (ΛΤ) is 25 ° C or more, and the viscosity value at the body temperature is true. (η at Tliq) is 15, 〇〇〇p〇ise or more, so that it has excellent glass forming ability to completely eliminate devitrification. 4. The softening point of the example changes within the range of 4 ° C, and the thermal expansion The number of sunspots (α) is slightly reduced, so 'it will increase the thermal shock resistance of the glass, and the raw alkalinity of the example of the chemical durability index of the glass of water, due to the addition of Β2〇3 The side of the stone-like salt shows the broken ring pain', which is greatly reduced compared with the comparative example, so 'increasing the long-term open-air use of the glass for the battery, the weather resistance of the rain, snow or atmospheric moisture, thereby increasing the solar energy. The life of the battery 6. The solar light transmittance (Tvis) of the embodiment is increased as compared with the comparative example to increase the photoelectric efficiency of the solar cell. This is related to the sale of Fe2〇3 which will be described later, and is used as in the embodiment. Alkali aluminum boron bismuth silicate The amount of Fe203 as an impurity can be greatly reduced without further refining process, so that the 'sun light transmittance of the embodiment' is relatively higher than that of the above. The formulation of the examples and comparative examples of the above [Table 2] will be used. The glass component obtained is expressed by weight in the following [Table 2]. The components produced by using only the refined raw materials shown in the comparative example of [Table 3] and one and the alkali-free aluminum boron lanthanum 17 S-201213267 acid were compared. When the salt shows the component of the example of the cullet as a raw material, in the case of the embodiment of the present invention, Al2〇3 is slightly increased, and Fe2〇3 is 0.02 part by weight of the comparative example mixed from the refined industrial raw material. In the case of the example, the weight fraction of the cullet is greatly reduced to 0.015 part by weight, and although the components of B2〇3, SrO, and Sn02 are mixed, as shown by the characteristics of [Table 2], not only the composition is not destroyed. The original characteristics of the glass at least maintain or improve the characteristics of the glass. [Table 3] Example Comparative Example Component 1 2 3 4 1 2 Si02 72.5 72.1 71.3 71.0 72.8 72.6 A] 2〇3 0.57 1.0 1.5 1.9 0.4 0.18 B2O3 0.3 0.6 0.9 1.1 0 0 Na20 13.9 13.8 13.7 13.6 14 14 Composition (parts by weight) K20 0.1 0.1 0.1 0.1 0.1 0.1 MgO 3.9 3.8 3.8 3.8 3.9 3.6 CaO 8.6 8.5 8.5 8.4 8.7 9.5 SrO 0.02 0.04 0.07 0.08 0 0 Fe2〇3 0.018 0.0169 0.0153 0.0142 0.018 0.02 Sn02 0.01 0.02 0.03 0.04 0 0 The above embodiments are only intended to illustrate the invention, but are not intended to be limiting, and those skilled in the art will understand that the invention may be modified, modified or substituted. Without departing from the spirit and scope of the invention, it is intended to be included within the scope of the invention. [Simple description of the diagram] (None) [Explanation of main component symbols] (None) 18